CN114180969B - Preparation method and application of nitrogen-containing high-entropy MAX phase material and two-dimensional material - Google Patents
Preparation method and application of nitrogen-containing high-entropy MAX phase material and two-dimensional material Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a nitrogen-containing high-entropy MAX phase material and a two-dimensional material, wherein the preparation method of the nitrogen-containing high-entropy MAX phase material comprises the following steps: the method comprises the steps of reacting a nitride of A, more than five simple substances or compounds of transition metals and the simple substances or compounds of A, or reacting a nitride of A, at least one simple substance or compound of transition metal and an M 'AX phase material without nitrogen, wherein the types of elements in the transition metal and the M' are more than five, so as to prepare the nitrogen-containing high-entropy MAX phase material. The preparation method disclosed by the invention is simple in process, low in cost and easy for industrial mass production, and lays a foundation for application of nitrogen-containing high-entropy MAX phase materials and two-dimensional materials.
Description
The present application claims priority from chinese patent application No. 202110560245.X entitled "preparation method and use of novel MAX phase and two-dimensional materials containing nitrogen" filed by the chinese patent office at 5 and 21 of 2021, the content of which is incorporated herein by reference.
Technical Field
The invention relates to the field of new materials, in particular to a preparation method and application of a nitrogen-containing high-entropy MAX phase material and a two-dimensional material.
Background
Layered transition metal carbides, nitrides and carbonitrides (MAX phase) have a rich chemical composition with the formula M n+1 AX n M represents early transition metal elements such as Sc, Y, ti, zr, hf, V, nb, ta, cr, mo and W, etc., A is mainly a group 13-16 element such as Al, si, P and S, etc., and X represents C and/or N element. From MAX phase materialSince strong coupling action exists between the 3d orbitals of the M metal atom and the 2p orbitals of the A atom, the electrical conductivity of the metal and the thermal conductivity of the ceramic are imparted to the MAX phase, the MAX phase is also called conductive ceramic. As far as 150 MAX phase materials are found, the nitrogen-containing MAX phase is concentrated in Ti only 2 AlN、Ti 2 AlC x N 1-x 、Ti 3 AlCN and Ti 4 AlN 3 Very few, high entropy MAX phases containing nitrogen (containing at least 5 transition metal elements) have not been reported to date. Accordingly, nitrogen-containing high-entropy two-dimensional materials are still not available. While the nitrogen-containing high-entropy materials that have been reported so far have been mainly focused on (Cr 0.2 Mo 0.2 Nb 0.2 V 0.2 Zr 0.2 ) N and (V) 0.2 Nb 0.2 Ta 0.2 Mo 0.2 W 0.2 ) N and other materials with three-dimensional block structures, such high-entropy nitrides have shown excellent mechanical, magnetic, high-temperature and corrosion resistance properties. Therefore, it is speculated that the nitrogen-containing high-entropy two-dimensional material tends to exhibit more excellent physicochemical properties. Therefore, development of a nitrogen-containing high-entropy two-dimensional material, a nitrogen-containing high-entropy MAX phase material and a preparation method thereof are needed.
At present, a common method for preparing MAX phase materials in the prior art is a high-temperature sintering method, which comprises the following steps: (1) mixing the elementary powders constituting the MAX phase in proportion; (2) Filling the powder mixture into an agate ball milling tank, and ball milling for a plurality of hours by using a ball mill; (3) And (3) placing the mixed powder after ball milling into an alumina crucible, and placing into a tube furnace for high-temperature sintering under the protection of argon. (4) And after the reaction is finished, cooling to room temperature, taking out a sample, grinding and sieving to obtain MAX phase powder. However, when the method is used for preparing the nitrogen-containing middle-entropy or high-entropy MAX phase material, as four or more than five transition metal simple substances are needed to be added, the transition metal simple substances are easy to react with the nitrogen-containing raw materials at high temperature to generate transition metal nitride particles with rock salt structures, so that the homogeneous middle-entropy or high-entropy MAX phase material cannot be prepared.
Disclosure of Invention
Aiming at the technical problem that a high-temperature sintering method in the prior art is difficult to prepare a homogeneous nitrogen-containing middle-entropy or high-entropy MAX phase material, the invention provides a preparation method of a nitrogen-containing MAX phase material, which comprises the following steps: taking an A nitride, more than four transition metal simple substances or compounds and an A simple substance or compound as raw materials for reaction to prepare a nitrogen-containing MAX phase material; wherein, A is selected from at least one of VIIB, VIII, I B, IIB, IIIA, IVA, VA and VIA group elements; or, taking an M' AX phase material containing A nitride, at least one transition metal simple substance or compound and no nitrogen as a raw material to react, so as to prepare the nitrogen-containing MAX phase material; wherein the element types in the transition metal and the M' are more than four, and the A is at least one element selected from VIIB, VIII, I B, IIB, IIIA, IVA, VA and VIA;
in some embodiments, the raw material further comprises an elemental X, wherein X is carbon or boron; and/or the variety of transition metal elements in the raw materials is five or six; and/or the compound of the transition metal is carbide.
In some embodiments, the transition metal and/or M' are each selected from Ti, zr, hf, V, nb, ta, cr, mo, W, fe, co, ni, pt, au, ag, pd, cu or Bi elements; preferably, the transition metal contains Ti element; and/or, the a is selected from Al, si, P, S, fe, cu, zn, ga, ge, as, cd, in, sn, tl, pb or Bi elements; and/or, X in the obtained nitrogen-containing MAX phase material is carbon and nitrogen.
In some embodiments, prior to performing the reaction, further comprising: grinding: grinding the raw materials; and/or, a pressing step: pressing the raw materials to form the composite material; preferably, the pressurizing pressure is between 10MPa and 50MPa.
In some embodiments, the temperature of the reaction is between 600 ℃ and 3000 ℃; preferably, between 1000 ℃ and 1700 ℃; and/or the reaction time is 1 h-20 h.
In some embodiments, the nitrogen-containing MAX phase material is prepared with an atomic ratio C: N of (1-x): x, wherein (0 < x < 1);
the invention also provides a preparation method of the nitrogen-containing two-dimensional material, which comprises the following steps: and (3) reacting the nitrogen-containing MAX phase material prepared by the preparation method with an etchant, and etching the component A to obtain the nitrogen-containing two-dimensional material.
In some embodiments, the etchant is one or more of a simple halogen, a halogen hydride, or a nitrogen hydride; or the etchant is hydrogen halide solution, acid solution and halide salt system or halogen metal salt.
In some embodiments, the reaction is a vapor phase process etch, and the etchant is in a vapor phase or is capable of being converted to a vapor phase for etching; and/or the thickness of the obtained lamellar layer of the nitrogenous two-dimensional material is between 2nm and 10 nm.
The invention also comprises application of the nitrogenous high-entropy AMX phase material or nitrogenous two-dimensional material obtained by the preparation method in catalysis, sensors, electronic devices, super capacitors, batteries, electromagnetic shielding, wave absorbing materials and corrosion resistant materials.
The method has the beneficial technical effects that the nitride of A is used as a reaction raw material, the nitride reacts with the transition metal element to produce the nitrogen-containing MAX phase material, the generated nitrogen-containing MAX phase material can also be used as a framework material to provide a matrix in which other transition metal elements are diffused, or the nitrogen-containing high-entropy MAX phase material is obtained through isomorphous displacement reaction among the MAX phase materials. According to the preparation method, the nitrogen-containing high-entropy MAX phase material is prepared, the A is etched by the etchant, the nitrogen-containing medium-entropy or high-entropy two-dimensional material (nitrogen-containing MXene material) is obtained, and a new kind is added for the two-dimensional material family. The preparation method disclosed by the invention is simple in process, low in cost and easy for industrial amplification production, lays a foundation for application of nitrogen-containing middle-entropy or high-entropy MAX phase materials and nitrogen-containing middle-entropy or high-entropy two-dimensional materials, and has wide application prospects in the fields of catalysis, sensors, electronic devices, supercapacitors, batteries, electromagnetic shielding, wave-absorbing materials, corrosion-resistant materials, superconducting materials and the like in the future.
Drawings
FIG. 1A nitrogen-containing high entropy MAX phase material (Ti) in example 1 of the present invention 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 SEM photographs of (2).
FIG. 2A nitrogen-containing high-entropy MAX phase material (Ti) in example 1 of the present invention 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 Is a XRD spectrum of (C).
FIG. 3A nitrogen-containing high-entropy MAX phase material (Ti) in example 2 of the present invention 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 SEM photographs of (2).
FIG. 4A nitrogen-containing high-entropy MAX phase material (Ti) in example 2 of the present invention 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 Is a XRD spectrum of (C).
FIG. 5A nitrogen-containing high-entropy two-dimensional material (Ti) in example 3 of the present invention 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 C 0.5 N 0.5 T x SEM photographs of (2).
FIG. 6A nitrogen-containing high-entropy two-dimensional phase material (Ti) in example 3 of the present invention 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 C 0.5 N 0.5 T x Is a XRD spectrum of (C).
FIG. 7A nitrogen-containing high-entropy two-dimensional material (Ti) in example 3 of the present invention 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 C 0.5 N 0.5 T x HRTEM and STEM photographs and primordial profiles of (c).
Detailed Description
The following detailed description of embodiments of the invention is, therefore, to be taken in conjunction with the accompanying drawings, and it is to be understood that the scope of the invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components.
The technical scheme of the invention is described below through specific examples. It is to be understood that the reference to one or more steps of the invention does not exclude the presence of other methods and steps before or after the described combined steps, or that other methods and steps may be interposed between these explicitly mentioned steps. It should also be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Unless otherwise indicated, the numbering of the method steps is for the purpose of identifying the method steps only and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention, which relative changes or modifications may be regarded as the scope of the invention which may be practiced without substantial technical content modification.
The raw materials and instruments used in the examples are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
The technical concept of the invention is that at least one transition metal simple substance or carbide reacts with nitride of A to generate nitrogen-containing MAX phase material, then the nitrogen-containing MAX phase material is taken as a framework, and a plurality of transition metal elements are diffused and doped into the nitrogen-containing MAX phase material to prepare the nitrogen-containing MAX phase material (medium-entropy or high-entropy MAX phase material), and the technical scheme comprises two implementation modes:
the method comprises the steps of (A) reacting nitride, more than four transition metal simple substances or compounds and simple substances or compounds of A to obtain nitrogen-containing medium-entropy or high-entropy MAX phase material, wherein A is at least one element selected from VIIB, VIII, I B, IIB, IIIA, IVA, VA and VIA. The mechanism of the reaction is explained as follows: the nitride of the A reacts with simple substance or carbide of the transition metal to generate a nitrogen-containing MAX phase material, then the nitrogen-containing MAX phase material is taken as a framework, and transition metal elements in the residual simple substance or carbide of the transition metal permeate into the nitrogen-containing MAX phase material under the condition of high temperature to obtain the nitrogen-containing high-entropy MAX phase material; or, the nitride of A reacts with simple substances or carbides of a plurality of transition metals to generate a plurality of nitrogen-containing MAX phase materials, and under the condition of high temperature, isomorphous displacement reaction is carried out among the plurality of nitrogen-containing MAX phase materials to obtain the homogeneous nitrogen-containing high-entropy MAX phase material. In the technical scheme, the nitride of the raw material A and the simple substance or carbide of the transition metal belong to industrial products, are easy to prepare and low in cost, can prepare the nitrogen-containing high-entropy MAX phase material through a high-temperature one-step method, and have industrial practical values.
And (II) taking a nitride of A, at least one simple substance or carbide of a transition metal element and at least one M ' AX phase material as raw materials for reaction, wherein the types of the transition metal element and M ' in the M ' AX phase in the raw materials are more than five, and the A is at least one element selected from VIIB, VIII, I B, IIB, IIIA, IVA, VA and VIA groups. The mechanism of the reaction is explained as follows: the nitride of A reacts with simple substance or carbide of a transition metal element to generate a nitrogen-containing MAX phase material, then the nitrogen-containing MAX phase material is taken as a framework, and under the condition of high temperature, the nitrogen-containing MAX phase material and M 'AX phase undergo isomorphous replacement reaction, and M' diffuses into the framework of the nitrogen-containing MAX phase material to obtain the nitrogen-containing high-entropy MAX phase material. In the technical scheme, the isomorphous substitution reaction of the MAX phase material is utilized, and the nitrogen-containing middle-entropy or high-entropy MAX phase material can be prepared.
Referring to definition of various metal alloy elements in the materialization, in the application, when M in the prepared nitrogen-containing MAX phase material is four metal elements, the nitrogen-containing MAX phase material is called as a medium-entropy MAX phase material, and when M is more than five metal elements, the nitrogen-containing MAX phase material is called as a high-entropy MAX phase material.
The nitrogen-containing middle-entropy or high-entropy MAX phase material prepared by the method belongs to one type of MAX phase material large family, and a series of middle-entropy or high-entropy MAX phase materials can be obtained by the method.
The nitrogen-containing MAX phase material prepared by the invention consists of M element, A element and X element, and the chemical general formula of the nitrogen-containing MAX phase material is M n+1 AX n Wherein the M element is at least four metal elements selected from IIIB, IVB, VB, VIB, VIIB, VIII, IB and IIB, the A element is at least one element selected from VIIB, VIII, I B, IIB, IIIA, IVA, VA and VIA, and the X element is nitrogen and at least one element selected from IIIA, IVA, VA and VIA is notA metal element; n is 1, 2, 3, 4, 5 or 6.
In some embodiments, the X element is carbon or nitrogen; the M element is selected from more than four of Ti, zr, hf, V, nb, ta, cr, mo, W, fe, co, ni, pt, au, ag, pd, cu or Bi elements; the A element is at least one selected from Al, si, P, S, fe, cu, zn, ga, ge, as, cd, in, sn, tl, pb and Bi elements.
In some embodiments, the number of M element types in the nitrogen-containing MAX phase material prepared above is four, five or six.
The nitrogen-containing two-dimensional material prepared by the method is obtained by etching the element A in the nitrogen-containing MAX phase material.
Example 1
The invention provides a method for preparing nitrogen-containing high-entropy MAX phase (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 The preparation method of (2) comprises the following steps:
and (3) proportioning: according to the chemical formula (Ti) of the high entropy MAX phase 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 The stoichiometric ratio (molar ratio) of Ti, nb, ta, V, zr, alN, al and graphite is adopted as raw material precursors, the molar ratio is that Ti, ta, V, zr and Al are respectively calculated according to the corresponding molar ratio, and the raw material precursors are accurately weighed;
grinding: placing the raw materials into a ball milling tank for ball milling at 600rpm for 20h, and placing the mixed powder into a powder tabletting mold for cold pressing treatment after ball milling, wherein the pressure is 20MPa and the pressurizing time is 5min;
and (3) sintering: transferring the ball-milled block into a corundum crucible, heating to 1500 ℃ at a speed of 5 ℃/min under Ar atmosphere, preserving heat for 1h, cooling along with a furnace, taking out the cooled block, and grinding to obtain a nitrogen-containing high-entropy MAX phase (Ti) 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 And (3) powder.
For nitrogen-containing high-entropy MAX phase material (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 Scanning Electron Microscope (SEM) test was performed, and the results are shown in FIG. 1, (Ti) 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 Has an irregular three-dimensional block structure, and is similar to the appearance of most of prepared MAX phases. For nitrogen-containing high-entropy MAX phase material (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 As a result of X-ray diffraction (XRD) analysis, as shown in FIG. 2, the raw material (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 Strong diffraction peaks appear in the XRD pattern, and (002) peaks appear at 12.9 degrees, indicating that the material has a layered structure and a synthetic nitrogen-containing high-entropy MAX phase (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 Diffraction pattern of (C) and reported quaternary MAX phase Ti 2 AlC 0.5 N 0.5 Consistent, and no other carbide and nitride impurity peaks appear, indicating that the resulting nitrogen-containing high entropy MAX phase (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 Is a single phase with high purity.
Example 2
The invention provides a method for preparing nitrogen-containing high-entropy MAX phase (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 The preparation method of (2) comprises the following steps:
and (3) proportioning: according to the chemical formula (Ti) of the nitrogen-containing high-entropy MAX phase 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 The stoichiometric ratio (molar ratio) of Ti, nb, ta, V, zr, tiC, nbC, taC, VC, zrC, alN and Al are used as raw material precursors, the molar ratio is Ti, nb, ta, V, zr, tiThe preparation method comprises the steps of (1) accurately weighing raw material precursors according to corresponding molar ratios, wherein (1) the raw material precursors comprise (1) NbC (TaC), VC (ZrC), alN (Al=0.3:0.3:0.3:0.3:0.3:0.3:0.1:0.1:0.1:0.1:0.5:0.7);
grinding: placing the raw materials into a ball milling tank for ball milling at 600rpm for 20h, and placing the mixed powder into a powder tabletting mold for cold pressing treatment after ball milling, wherein the pressure is 20MPa and the pressurizing time is 5min;
and (3) sintering: transferring the ball-milled block into a corundum crucible, heating to 1500 ℃ at a speed of 5 ℃/min under Ar atmosphere, preserving heat for 1h, cooling along with a furnace, taking out the cooled block, and grinding to obtain a nitrogen-containing high-entropy MAX phase (Ti) 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 And (3) powder.
For nitrogen-containing high-entropy MAX phase material (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 Scanning Electron Microscope (SEM) test was performed, and the results are shown in FIG. 3, (Ti) 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 Has an irregular three-dimensional block structure, and is similar to the appearance of most of prepared MAX phases. For nitrogen-containing high-entropy MAX phase material (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 As a result of X-ray diffraction (XRD) analysis, as shown in FIG. 4, the raw material (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 Strong diffraction peaks appear in the XRD pattern, and (002) peaks appear at 12.9 degrees, indicating that the material has a layered structure and a synthetic nitrogen-containing high-entropy MAX phase (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 Diffraction pattern of (C) and reported quaternary MAX phase Ti 2 AlC 0.5 N 0.5 Consistent, and no other carbide and nitride impurity peaks appear, indicating that the resulting nitrogen-containing high entropy MAX phase (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 Is a single phase with high purity.
Example 3
This example provides a specific example of vapor etching of nitrogen-containing high-entropy MAX to produce a high-entropy two-dimensional material, with nitrogen-containing high-entropy MAX phase (Ti) produced in example 1 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 As a precursor, commercial liquefied HCl gas is used as an etchant to prepare a two-dimensional material by reaction, and a selected reactor is a tube furnace, and the method comprises the following steps:
1) Placing powdered (Ti in the tube furnace 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 ；
2) Filling HI gas into the tubular furnace for a period of time, and sealing the reaction cavity after the reaction cavity in the reaction device is filled with HI gas;
3) Heating the interior of the reaction device to 700 ℃, preserving heat for 30min, and performing etching reaction to obtain a target product high-entropy two-dimensional material (Ti) 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 C 0.5 N 0.5 T x 。
And taking out the target product after the reaction device is naturally cooled to room temperature. Couple (Ti) 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 High entropy two-dimensional material (Ti after reaction with HCl 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 C 0.5 N 0.5 T x SEM test of two target products is carried out, and the result is shown in FIG. 5, and the reacted target product is an accordion layered structure which has ultrathin two-dimensional nano-sheets stacked layer by layer, which is obviously different from the raw materials (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 Layered bulk morphology (fig. 1). Couple (Ti) 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 And nitrogen-containing high entropy MXene (Ti) 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 C 0.5 N 0.5 T x XRD analysis was performed, and the results are shown in FIG. 6, in which, by comparison, the raw material (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 The (002) peak in (a) appears at the 12.9 DEG position, and the (002) peak in the target product after the reaction with HI gas is shifted to 7.2 DEG at a low angle, which indicates that HI gas etches (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 Al element in the alloy, a lamellar structure of high-entropy two-dimensional material (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 C 0.5 N 0.5 T x Resulting in an expansion of the interlayer spacing, consistent with scanning electron micrograph results. Target product high entropy two-dimensional material (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 C 0.5 N 0.5 T x In STEM photo of (c) there are a large number of two-dimensional ultrathin nanoplatelets, as shown in fig. 7, indicating that the accordion (Ti 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 C 0.5 N 0.5 T x A large number of two-dimensional nano sheets can be obtained through simple stripping, and the high-entropy two-dimensional material (Ti) prepared by the embodiment has a good single crystal structure and is tested through an atomic force microscope AFM 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 C 0.5 N 0.5 T x The thickness of (2) is between 2nm and 3 nm.
Example 4
The present embodiment provides another method for preparing a nitrogen-containing high-entropy two-dimensional material, which adopts the nitrogen-containing high-entropy MAX phase material prepared in the embodiments 1 to the steps of:
50ml of 48% hydrofluoric acid (HF) was used as an etchant, and 1g of step (1) was takenThe nitrogen-containing high-entropy MAX phase obtained in example 1 was placed in an etchant, reacted at 50℃for 48 hours, and after the reaction was completed, subjected to centrifugal separation, water washing and drying to obtain a nitrogen-containing high-entropy two-dimensional material (Ti) 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 C 0.5 N 0.5 T x (wherein T x Representing the functional group contained).
In some embodiments, the etchant may also be selected to be one or more of a simple halogen, a halogen hydride, or a nitrogen hydride, such as: br (Br) 2 、I 2 、HBr、NH 3 Or pH of 3 Etc. In the etching process, the gas phase etchant can enter the etched MAX phase to more fully etch the A phase in the MAX phase to obtain the high-entropy two-dimensional material sheet layer (2 nm-10 nm) with an ultrathin structure. In addition, the gas phase method etching does not contain solid impurities, so that the powder material of the high-entropy two-dimensional sheet layer can be directly obtained, complex processes such as purification, drying and the like of liquid phase etching are avoided, industrial batch preparation can be realized, the preparation cost of the high-entropy two-dimensional sheet layer material can be reduced, and the method has great commercial value.
In some embodiments, liquid phase etchants of the prior art may also be employed, including: a hydrogen halide solution, an acid solution + halide salt system, or a halide metal salt.
Example 5
This example provides another method for preparing nitrogen-containing medium entropy MAX phase (Ti 0.25 Nb 0.25 Ta 0.25 V 0.25 ) 2 AlC 0.75 N 0.25 The preparation method of (2) comprises the following steps:
and (3) proportioning: according to the chemical formula (Ti) of the nitrogen-containing high-entropy MAX phase 0.2 Nb 0.2 Ta 0.2 Zr 0.2 V 0.2 ) 2 AlC 0.5 N 0.5 In the stoichiometric ratio (molar ratio) of Ti, alN, nb 2 AlC、Ta 2 AlC、V 2 AlC is used as a raw material precursor, and the molar ratio of AlC to AlN to Nb is Ti 2 AlC:Ta 2 AlC:V 2 AlC＝2:1:1:1:1；
Grinding: placing the raw materials into a ball milling tank for ball milling at 600rpm for 20h, and placing the mixed powder into a powder tabletting mold for cold pressing treatment after ball milling, wherein the pressure is 20MPa and the pressurizing time is 5min;
and (3) sintering: transferring the ball-milled block into a corundum crucible, heating to 1200 ℃ at a speed of 5 ℃/min under Ar atmosphere, preserving heat for 1h, cooling along with a furnace, taking out the cooled block, and grinding to obtain a nitrogen-containing medium entropy MAX phase (Ti) 0.25 Nb 0.25 Ta 0.25 V 0.25 ) 2 AlC 0.75 N 0.25 And (3) powder.
In the preparation method, the simple substance of the raw material transition metal is preferable, more preferably, the simple substance of the transition metal contains metal Ti element, in the transition metal element, the metal Ti element can react with nitride of A at a relatively low temperature (1200 ℃ -1400 ℃) to generate nitrogen-containing MAX phase material, the nitrogen-containing MAX phase material is taken as a framework, and other types of transition metal elements are diffused into the nitrogen-containing MAX phase material, so that the nitrogen-containing middle-entropy or high-entropy MAX phase material is obtained.
Example 6
The embodiment provides another preparation method of a nitrogen-containing high-entropy MAX phase, which comprises the following steps:
and (3) proportioning: according to the chemical formula (Ti) of the high entropy MAX phase 1/6 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 Hf 1/6 ) 2 AlC 0.5 N 0.5 The stoichiometric ratio (molar ratio) of Ti, alN, hfC, V, al, (Nb) 1/3 Ta 1/3 Zr 1/3 ) 2 AlC is used as a raw material precursor, and the molar ratio of AlC to AlN to Hf to V to Al (Nb) 1/3 Ta 1/3 Zr 1/3 ) 2 Alc=1.3:2:1.3:1.3:1.3:2, each raw material precursor is determined;
grinding: manually grinding the raw materials in a mortar for 10min, and placing the mixed powder in a powder tabletting mold for cold pressing treatment after grinding, wherein the pressure is 20MPa and the pressurizing time is 5min;
and (3) sintering: transferring the ball-milled blocks into a corundum crucibleHeating to 1400 ℃ at 5 ℃/min under Ar atmosphere, preserving heat for 1h, heating to 1800 ℃ and preserving heat for 1h, cooling with a furnace, taking out the cooled block, and grinding to obtain nitrogen-containing high-entropy MAX phase (Ti) 1/6 Nb 1/6 Ta 1/6 Zr 1/6 V 1/6 Hf 1/6 ) 2 AlC 0.5 N 0.5 And (3) powder.
It should be noted that the complex reaction occurs in the high-temperature sintering process, the heating temperature can be within 1000 ℃ to 3000 ℃, the optimal conditions of different kinds of MAX phase materials can be determined through limited experiments, and the optimized process can be obtained, for example, the reaction can be controlled in a sectional heating mode.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (13)
1. The preparation method of the nitrogen-containing high-entropy MAX phase material is characterized by comprising the following steps of:
taking an A nitride, more than five transition metal simple substances or compounds and an A simple substance or compound as raw materials for reaction to prepare a nitrogen-containing high-entropy MAX phase material; wherein A is an Al element, and the compound of the transition metal is carbide;
or, taking an M' AX phase material containing A nitride, at least one transition metal simple substance or compound and no nitrogen as a raw material to react, so as to prepare the nitrogen-containing high-entropy MAX phase material; the transition metal and the M' are more than five types of elements, wherein A is an Al element, and the compound of the transition metal is carbide;
when the transition metal is added into the raw material in a simple substance state, the raw material also comprises an X simple substance, wherein X is carbon or boron element.
2. The method of claim 1, wherein when the feedstock comprises a transition metal carbide, the feedstock further comprises elemental X, wherein X is carbon or boron;
and/or the variety of the transition metal elements in the raw materials is five or six.
3. The production method according to claim 1 or 2, wherein the transition metal or the M' is selected from Ti, zr, hf, V, nb, ta, cr, mo, W, fe, co, ni, pt, au, ag, pd, cu or Bi element;
and/or, X in the obtained nitrogen-containing high-entropy MAX phase material is carbon and nitrogen.
4. The method of claim 3, wherein said transition metal comprises Ti.
5. The method of preparing as claimed in claim 1, further comprising, prior to performing the reaction:
grinding: grinding the raw materials;
and/or, a pressing step: and pressing the raw materials to form the product.
6. The method according to claim 5, wherein in the pressing step, the pressing is performed under a pressing pressure of 10MPa to 50MPa.
7. The method of claim 1, wherein the temperature of the reaction is between 600 ℃ and 3000 ℃;
and/or the reaction time is 1-20 h.
8. The method of claim 7, wherein the temperature of the reaction is between 1000 ℃ and 1700 ℃.
9. The process according to claim 3, wherein the nitrogen-containing high-entropy MAX phase material obtained by the process has an atomic ratio C: N of (1-x): xWherein, (0)< x< 1)。
10. The preparation method of the nitrogen-containing two-dimensional material is characterized by comprising the following steps:
the nitrogen-containing high-entropy MAX phase material prepared by the preparation method of any one of claims 1 to 9 is reacted with an etchant, and the component A is etched to obtain the nitrogen-containing two-dimensional material.
11. The method of claim 10, wherein the etchant is one or more of a simple halogen, a halogen hydride, or a nitrogen hydride;
or the etchant is hydrogen halide solution, acid solution and halide salt system or halogen metal salt.
12. The method of claim 10, wherein the reaction is a gas phase process etch, and the etchant is in a gas phase or is capable of being converted to a gas phase for the etch;
and/or the thickness of the obtained lamellar layer of the nitrogenous two-dimensional material is between 2nm and 10 nm.
13. Use of a nitrogen-containing high-entropy MAX-phase material obtained according to the preparation method of any one of claims 1 to 9 or a nitrogen-containing two-dimensional material obtained according to the preparation method of any one of claims 10 to 12 in catalysis, sensors, electronic devices, supercapacitors, batteries, electromagnetic shielding, wave-absorbing materials, corrosion-resistant materials.
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